Catalyst compositions comprising rhodium catalyst complexes

ABSTRACT

The present invention relates to catalyst compositions and methods for the preparation thereof. More particularly, the present invention relates to novel rhodium catalyst complexes compositions useful the crosslinking of compositions containing methylhydrogensiloxanes. The present invention further relates to a method for the preparation of these novel catalyst complexes and to their use in emulsions of methylhydrogensiloxanes which are used to treat fibers or fabrics.

BACKGROUND OF THE INVENTION

The present invention relates to catalyst compositions and to methodsfor the preparation thereof. More particularly, the present inventionrelates to novel rhodium catalyst complexes useful in the crosslinkingof compositions containing methylhydrogensiloxanes. The presentinvention further relates to a method for the preparation of these novelcatalyst complexes and to their use in emulsions ofmethylhydrogensiloxanes which are used to treat fibers or fabrics.

Compositions containing an unsaturated acetate and a rhodium catalysthave been described in the art. For example, Revis in U.S. Pat. Nos.4,954,401 and 5,082,735 discloses a process of curing and crosslinkingmethylhydrogensiloxanes by contacting and forming a mixture of an allylester with at least one methylhydrogensiloxane in the presence of aGroup VIII metal catalyst, and heating the mixture of the allyl ester,the methylhydrogensiloxane, and the Group VIII metal catalyst, in thepresence of ambient moisture until the methylhydrogensiloxane becomescured and crosslinked. The preferred catalyst is disclosed as beingRhCl₃.

Revis in U.S. Pat. No. 4,954,597 discloses a coating for a papersubstrate produced by contacting and forming a mixture of an allyl esterwith at least one methylhydrogensiloxane in the presence of a Group VIIImetal catalyst, and heating the mixture of the allyl ester, themethylhydrogensiloxane, the substrate and the Group VIII metal catalyst,in the presence of ambient moisture until the methylhydrogensiloxanebecomes cured and crosslinked. The preferred Group VIII metal catalystis disclosed as being RhCl₃.

Revis in U.S. Pat. No. 4,746,750 discloses a process for preparing silylketene acetals from allyl 2-organoacrylates comprising contacting anallyl 2-organoacrylate with a trisubstituted silane in the presence of arhodium catalyst such as RhCl₃.3H₂ O and separating and isolating thesilyl ketene acetal.

The present invention further relates to fiber treatment compositionscontaining the catalyst compositions of the instant invention.Compositions containing rhodium catalysts in combination withorganohydrogenpolysiloxanes have also been disclosed. For example,Chandra et al. in U.S. Pat. No. 3,690,810 discloses a process forcoating a surface with an organosiloxane composition to render itnon-adherent, the organosiloxane composition is disclosed as beingsubstantially solvent-free, having a viscosity not exceeding 4,000 cS at25° C., and comprising (1) a polydiorganosiloxane having silicon-bondedvinyl radicals, (2) an organohydrogenpolysiloxane, and a catalyst havingthe formulae RhX₃ (SR₂)₃ or Rh₂ (CO)₄ X₂ in which X is a halogen,preferably chlorine, and each R is alkyl, aryl, aralkyl, alkylaryl orR'₃ SiQ wherein Q is a divalent aliphatic hydrocarbon radical and R' isalkyl, aryl, aralkyl, alkylaryl or (CH₃)₃ Si--.

Garden in U.S. Pat. No. 4,281,093 discloses a catalyst compositioncomprising a solution of an organometallic complex of platinum orrhodium in a liquid allyl ether which has a boiling point of at least150° C. at 1 bar and which is free from groups having an adverse effecton the catalytic affect of the complex; polyorganosiloxane coatingcompositions containing a Si--H polysiloxane and a polysiloxanecontaining Si--OH, Si-vinyl, or Si-allyl groups, an organometalliccomplex of platinum or rhodium, and an allyl ether as defined above; andthe use of the compositions for preparing release coatings onsubstrates.

Chen et al., in U.S. Pat. No. 5,063,260 discloses curable siliconecompositions which impart beneficial characteristics to fibers, thecompositions comprising an amino organofunctional substantially linearpolydiorganosiloxane polymer, a blend of an epoxy organofunctionalsubstantially linear polydiorganosiloxane polymer and a carboxylic acidorganofunctional substantially linear polydiorganosiloxane polymer, andan aminoorganosilane. Chen et al. also discloses a process for thetreatment of animal, cellulosic, and synthetic fibers by applying thecomposition described above the fiber and thereafter curing thecomposition on the fiber to obtain a treated fiber.

Yang in European Patent Application No. 0415254 discloses stable aqueousemulsion compositions containing an aminofunctional polyorganosiloxanecontaining at least two amino functionalized groups per molecule, one ormore silanes and optionally a hydroxy terminated polydiorganosiloxane,textiles treated with the emulsion compositions, and processes for thepreparation of the emulsion compositions.

Bunge in U.S. Pat. No. 4,954,554 discloses aqueous emulsionscompositions consisting essentially of a curable silicone compositioncomprising organopolysiloxane having silicon-bonded hydroxyl radicals orsilicon-bonded olefinic radicals, an organohydrogenpolysiloxane and acuring catalyst, a polyvinylalcohol emulsifying agent having a degree ofhydrolysis of 90 mole percent or more, and water. These compositions aredisclosed as having improved gloss and/or water-repellency and/oradhesive release.

Other silicone emulsions containing olefinic siloxanes have beendisclosed. For example, Hara et al. in U.S. Pat. Nos. 5,095,067 and5,104,927 teaches a release silicone emulsion composition comprising 100parts by weight of a specific organovinylpolysiloxane, from 1 to 50parts by weight of a specific organohydrogensiloxane, from 0.5 to 5parts of a platinum catalyst having a viscosity of 10 centistokes orless at 25° C., from 1.5 to 15 parts by weight of a nonionic emulsifyingagent having an average HLB of from 10 to 20, and a Ph of 6.5 or less,and water. These compositions are disclosed as having good pot life,curability and that the cured film has good release properties andresidual adhesive properties of adhesives.

However, none of the references hereinabove disclose a rhodium catalystcomposition comprising a rhodium catalyst, an unsaturated acetate, andan alcohol having 3 or more carbon atoms or a siloxane compositioncontaining such a catalyst.

SUMMARY OF THE INVENTION

This invention relates to novel rhodium catalyst complex compositionscomprising (A) a rhodium catalyst, (B) an unsaturated acetate, and (C)alcohols having having 3 or more carbon atoms.

The present invention further relates to method of making a rhodiumcatalyst complex, the method comprising the steps of (I) mixing: (A)rhodium catalyst, (B) an alcohol having 3 or more carbon atoms, and (C)an unsaturated acetate.

The present invention also relates to fiber treatment compositionscomprising (A) a rhodium catalyst, (B) an unsaturated acetate, (C)alcohols having having 3 or more carbon atoms, and (D) at least onemethylhydrogensiloxane. The fiber treatment compositions can furthercomprise (E) an organosilicon compound having an average of at least onegroup per molecule selected from the group consisting of hydroxy groups,carboxy groups, ester groups, amino groups, acetoxy groups, sulfogroups, alkoxy groups, acrylate groups, epoxy groups, fluoro groups,ether groups, olefinic hydrocarbon or halohydrocarbon radicals havingfrom 2 to 20 carbon atoms, and mixtures thereof.

According to the present invention it has been surprisingly discoveredthat commercially available rhodium catalysts can be complexed withunsaturated acetates and alcohols which can be useful for thecrosslinking of methylhydrogensiloxanes. These catalysts areparticularly effective in the crosslinking of emulsions ofmethylhydrogensiloxanes which are then applied to textile fibersubstrates.

It is an object of this invention to provide novel rhodium catalystcomplexes for the crosslinking of compositions containingmethylhydrogensiloxanes.

It is also an object of this invention to improve the heat age stabilityof emulsions containing methylhydrogensiloxanes.

It is an additional object of this invention to provide novel rhodiumcatalyst complexes which improve the flow out, slickness, softness, andcompression resistance of emulsions containing methylhydrogensiloxaneson textile substrates.

These and other features, objects and advantages of the presentinvention will be apparent upon consideration of the following detaileddescription of the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to rhodium catalyst complex compositionscomprising (A) a rhodium catalyst, (B) an unsaturated acetate, and (C)alcohols having having 3 or more carbon atoms.

Component (A) in the catalyst compositions of the present invention is arhodium catalyst. The preferred rhodium catalysts are rhodium catalystswith inorganic ligands. The preferred rhodium catalysts as Component (A)for the compositions of the present invention are RhCl₃, RhBr₃, and RhI₃and complexes thereof. Thus the rhodium catalyst with inorganic ligandscan be, for example, RhCl₃.nH₂ O, RhBr₃.nH₂ O, Rh(NO₃)₃.nH₂ O, orRh(SO₄)₃.nH₂ O wherein n has a value of from 1 to 10. Preferred asrhodium catalysts for the present invention are RhCl₃.3H₂, RhCl₃. 6H₂ O,RhBr₃.3H₂ O, and RhBr₃.6H₂ O.

The amount of rhodium catalyst, Component (A), that are used in thecompositions of this invention is not narrowly limited and can bereadily determined by one skilled in the art by routine experimentation.However, the most effective concentration of rhodium metal catalyst hasbeen found to be from about one part per million to about two thousandparts per million on a weight basis relative to the unsaturated acetateof Component (B).

Component (B) in the catalyst compositions of the instant invention isan unsaturated acetate. The unsaturated acetate can be an allyl ester orvinyl ester such as allyl butyrate, allyl acetate, linallyl acetate,allyl methacrylate, vinyl acetate, allyl acrylate, vinyl butyrate,isopropenyl acetate, vinyl trifluoroacetate, 2-methyl-1-butenyl acetate,vinyl 2-ethyl hexanoate, vinyl 3,5,5-trimethylhexanoate, allyl3-butenoate, bis-(2-methylallyl) carbonate, diallyl succinate, ethyldiallylcarbamate, and other known allyl esters. It is preferred for thecompositions of the instant invention that the unsaturated acetate isselected from the group consisting of allyl acetate, linallyl acetate,and isopropenyl acetate.

The amount of Component (B) employed in the compositions of the presentinvention varies depending on the amount of rhodium catalyst (A) andalcohol (C) is employed. It is preferred for purposes of this inventionthat the molar amount of unsaturated acetate is equal to or greater thanthe molar amount of rhodium catalyst. It is preferred for the instantinvention that Component (B) be used in a molar amount equal to themolar amount of rhodium catalyst to as much as ten times greater thanthe molar amount of rhodium catalyst employed.

Component (C) in the catalyst compositions of the instant invention arealcohols having having 3 or more carbon atoms. For the compositions ofthe instant invention any alcohol containing at least 3 carbon atoms issuitable. For example, C₃ and greater diols, furans having at least oneOH group per molecule, and pyrans having at least one OH group permolecule are suitable for use as Component (C) in the catalystcompositions of the present invention. The diols which can be used asthe alcohol in the instant invention are exemplified by 1,2-propanediol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol,1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol,1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, and2-phenyl-1,2-propanediol. Other alcohols suitable for use as Component(C) of the instant invention include 1-hexanol, 1-heptanol, benzylalcohol, 1-octanol, 1-nonanol, 1-decanol, undecylenyl alcohol,2,4-dichlorobenzyl alcohol, phenethyl alcohol, 1-undecanol,2-methylbenzyl alcohol, 3-methylbenzyl alcohol, and 2-phenyl-1-propanol.Examples of OH-containing furans and pyrans which are suitable for useas Component (C) in the compositions of the instant invention include5-methyl tetrahydrofuran-2-methanol, 2-hydroxy-2-(hydroxymethyl)tetrahydrofuran, dihydro-5 -(hydroxymethyl)-2-(3H)-furone,tetrahydropyran-2-methanol, tetrahydro-3-furan methanol, furfurylalcohol, and tetrahydrofurfuryl alcohol.

The amount of Component (C) employed in the compositions of the presentinvention varies depending on the amount of rhodium catalyst (A) andunsaturated acetate (B) is employed. It is preferred for purposes ofthis invention that the molar amount of (C) is equal to or greater thanthe molar amount of rhodium catalyst (A). It is preferred for theinstant invention that Component (C) be used in a molar amount equal tothe molar amount of rhodium catalyst to as much as 1000 times greaterthan the molar amount of rhodium catalyst employed. It is furtherpreferred in the present invention that an amount sufficient to dissolverhodium catalyst (A) is employed.

The catalyst compositions of this invention can be prepared byhomogeneously mixing Components (A), (B), and (C) and any optionalcomponents in any order. Thus it is possible to mix all components inone mixing step immediately prior to using the catalyst compositions ofthe present invention.

The present invention further relates to a method of making a rhodiumcatalyst complex, the method comprising the steps of (I) mixing: (A)rhodium catalyst, (B) an unsaturated acetate, and (C) an alcohol having3 or more carbon atoms, The rhodium catalyst (A), unsaturated acetate(B), and alcohol having 3 or more carbon atoms (C) are as delineatedabove including preferred amounts and embodiments thereof.

The present invention also relates to fiber treatment compositionscomprising (A) a rhodium catalyst, (B) an unsaturated acetate, (C)alcohols having having 3 or more carbon atoms, and (D) at least oneorganohydrogensiloxane. The rhodium catalyst (A), unsaturated acetate(B), and alcohol having 3 or more carbon atoms (C) are as delineatedabove including preferred amounts and embodiments thereof.

Component (D) in the fiber treatment compositions of the presentinvention is at least one organohydrogensilicon compound which is freeof aliphatic unsaturation and contains two or more silicon atoms linkedby divalent radicals, an average of from one to two silicon-bondedmonovalent radicals per silicon atom and an average of at least one, andpreferably two, three or more silicon-bonded hydrogen atoms per moleculethereof. Preferably the organohydrogensiloxane in the compositions ofthe present invention contains an average of three or moresilicon-bonded hydrogen atoms such as, for example, 5, 10, 20, 40, 70,100, and more.

The organohydrogenpolysiloxane is preferably a compound having theaverage unit formula R_(a) ¹ H_(b) SiO.sub.(4-a-b)/2 wherein R¹ denotessaid monovalent radical free of aliphatic unsaturation, the subscript bhas a value of from greater than 0 to 1, such as 0,001, 0.01, 0.1 and1.0, and the sum of the subscripts a plus b has a value of from 1 to 3,such as 1.2, 1.9 and 2.5. Siloxane units in theorganohydrogenpolysiloxanes having the average unit formula immediatelyabove have the formulae R₃ ³ SiO_(1/2), R₂ ³ HSiO_(1/2), R₂ ³ SiO_(2/2),R³ HSiO_(2/2), R³ SiO_(3/2), HSiO_(3/2) and SiO_(4/2). Said siloxaneunits can be combined in any molecular arrangement such as linear,branched, cyclic and combinations thereof, to provideorganohydrogenpolysiloxanes that are useful as component (D) in thecompositions of the present invention.

A preferred organohydrogenpolysiloxane for the compositions of thisinvention is a substantially linear organohydrogenpolysiloxane havingthe formula XR₂ SiO(XRSiO)_(c) SiR₂ X wherein each R denotes amonovalent hydrocarbon or halohydrocarbon radical free of aliphaticunsaturation and having from 1 to 20 carbon atoms. Monovalenthydrocarbon radicals include alkyl radicals, such as methyl, ethyl,propyl, butyl, hexyl, and octyl; cycloaliphatic radicals, such ascyclohexyl; aryl radicals, such as phenyl, tolyl, and xylyl; aralkylradicals, such as benzyl and phenylethyl. Highly preferred monovalenthydrocarbon radical for the silicon-containing components of thisinvention are methyl and phenyl. Monovalent halohydrocarbon radicalsfree of aliphatic unsaturation include any monovalent hydrocarbonradical noted above which is free of aliphatic unsaturation and has atleast one of its hydrogen atoms replaced with a halogen, such asfluorine, chlorine, or bromine. Preferred monovalent halohydrocarbonradicals have the formula C_(n) F_(2n+1) CH₂ CH₂ -- wherein thesubscript n has a value of from 1 to 10, such as, for example, CF₃ CH₂CH₂ -- and C₄ F₉ CH₂ CH₂ --. The several R radicals can be identical ordifferent, as desired. Additionally, each X denotes a hydrogen atom oran R radical. Of course, at least two X radicals must be hydrogen atoms.The exact value of y depends upon the number and identity of the Rradicals; however, for organohydrogenpolysiloxanes containing onlymethyl radicals as R radicals c will have a value of from about 0 toabout 1000.

In terms of preferred monovalent hydrocarbon radicals, examples oforganopolysiloxanes of the above formulae which are suitable as theorganohydrogensiloxane for the compositions of this invention includeHMe₂ SiO(Me₂ SiO)_(c) SiMe₂ H, (HMe₂ SiO)₄ Si, cyclo(MeHSiO)_(c), (CF₃CH₂ CH₂)MeHSiO{Me(CF₃ CH₂ CH₂)SiO}_(c) SiHMe(CH₂ CH₂ CF₃), Me₃SiO(MeHSiO)_(c) SiMe₃, HMe₂ SiO(Me₂ SiO)₀.5c (MeHSiO)₀.5c SiMe₂ H, HMe₂SiO(Me₂ SiO)₀.5c (MePhSiO)₀.1c (MeHSiO)₀.4c SiMe₂ H, Me₃ SiO(Me₂SiO)₀.3c (MeHSiO)₀.7c SiMe₃ and MeSi(OSiMe₂ H)₃organohydrogenpolysiloxanes that are useful as Component (D).

Highly preferred linear organohydrogenpolysiloxanes for the method ofthis invention have the formula YMe₂ SiO(Me₂ SiO)_(p) (MeYSiO)_(q) SiMe₂Y wherein Y denotes a hydrogen atom or a methyl radical. An average ofat least two Y radicals per molecule must be hydrogen atoms. Thesubscripts p and q can have average values of zero or more and the sumof p plus q has a value equal to c, noted above. The disclosure of U.S.Pat. No. 4,154,714 shows highly-preferred organohydrogenpolysiloxanes.

Especially preferred as Component (D) are methylhydrogensiloxanesselected from the group consisting ofbis(trimethylsiloxy)dimethyldihydrogendisiloxane,diphenyldimethyldisiloxane, diphenyltetrakis(dimethylsiloxy)disiloxane,heptamethylhydrogentrisiloxane, hexamethyldihydrogentrisiloxane,methylhydrogencycosiloxanes, methyltris(dimethylhydrogensiloxy)silane,pentamethylpentahydrogencyclopentasiloxane,pentamethylhydrogendisiloxane, phenyltris(dimethylhydrogensiloxy)silane,polymethylhydrogensiloxane, tetrakis(dimethylhydrogensiloxy)silane,tetramethyltetrahydrogencyclotetrasiloxane,tetramethyldihydrogendisiloxane, and methylhydrogendimethylsiloxanecopolymers.

The amount of Component (D) employed in the compositions of the presentinvention varies depending on the amount of unsaturated acetate, rhodiumcatalyst, and alcohol employed. It is preferred for purposes of thisinvention that from 40 to 99.5 weight percent of Component (D) be used,and it is highly preferred that from 70 to 90 weight percent ofComponent (D) be employed, said weight percent being based on the totalweight of the composition.

The fiber treatment compositions can further comprise (E) anorganosilicon compound having an average of at least one group permolecule selected from the group consisting of hydroxy groups, carboxygroups, ester groups, amino groups, acetoxy groups, sulfo groups, alkoxygroups, acrylate groups, epoxy groups, fluoro groups, ether groups,olefinic hydrocarbon or halohydrocarbon radicals having from 2 to 20carbon atoms, and mixtures thereof. It is preferred for purposes of thepresent invention that Component (E) is a compound having its formulaselected from the group consisting of (i) R¹ ₃ SiO(R² SiO)_(x) (R¹RSiO)_(y) SiR¹ ₃, (ii) R₂ R¹ SiO(R² SiO)_(x) (R¹ RSiO)_(y) SiR₂ R¹,(iii) RR¹ ₂ SiO(R² SiO)_(x) (R¹ RSiO)_(y) SiRR¹ ₂, wherein R is amonovalent hydrocarbon or halohydrocarbon radical having from 1 to 20carbon atoms, R¹ is a group selected from the group consisting ofhydroxy groups, carboxy groups, ester groups, amino groups, acetoxygroups, sulfo groups, alkoxy groups, acrylate groups, epoxy groups,fluoro groups, ether groups, olefinic hydrocarbon or halohydrocarbonradicals having from 2 to 20 carbon atoms, and mixtures thereof, x has avalue of 0 to 3000, and y has a value of 1 to 100.

The monovalent radicals of R in Component (E) can contain up to 20carbon atoms and include halohydrocarbon radicals free of aliphaticunsaturation and hydrocarbon radicals. Monovalent hydrocarbon radicalsinclude alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, andoctyl; cycloaliphatic radicals, such as cyclohexyl; aryl radicals, suchas phenyl, tolyl, and xylyl; aralkyl radicals, such as benzyl andphenylethyl. Highly preferred monovalent hydrocarbon radical for thesilicon-containing components of this invention are methyl and phenyl.Monovalent halohydrocarbon radicals include any monovalent hydrocarbonradical noted above which has at least one of its hydrogen atomsreplaced with a halogen, such as fluorine, chlorine, or bromine.Preferred monovalent halohydrocarbon radicals have the formula C_(n)F_(2n+1) CH₂ CH₂ -- wherein the subscript n has a value of from 1 to 10,such as, for example, CF₃ CH₂ CH₂ -- and C₄ F₉ CH₂ CH₂ --. The several Rradicals can be identical or different, as desired and preferably atleast 50 percent of all R radicals are methyl.

The functional groups of R¹ are selected from the group consisting ofhydroxy groups, carboxy groups, ester groups, amino groups, acetoxygroups, sulfo groups, alkoxy groups, acrylate groups, epoxy groups,fluoro groups, ether groups, olefinic hydrocarbon or halohydrocarbonradicals having from 2 to 20 carbon atoms, and mixtures thereof. Hydroxygroups suitable for use in the compositions of the instant inventioninclude hydroxyalkyl groups, hydroxyaryl groups, hydroxycycloalkylgroups, and hydroxycycloaryl groups. Preferred hydroxy (OH) groups as R¹in the compositions of this invention include groups such as hydroxy,hydroxypropyl, hydroxybutyl, hydroxyphenyl, hydroxymethylphenyl,hydroxyethylphenyl, and hydroxycyclohexyl.

Carboxy groups suitable for use as R¹ in the compositions of the instantinvention include carboxyalkyl groups, carboxyaryl groups,carboxycycloalkyl groups, and carboxycycloaryl groups. Preferred carboxygroups as R¹ in the compositions of this invention include groups suchas carboxy, carboxymethyl, carboxyethyl, carboxypropyl, carboxybutyl,carboxyphenyl, carboxymethylphenyl, carboxyethylphenyl, andcarboxycyclohexyl.

Ester groups can also be used as R¹ in the formulae hereinabove. Theseester groups can include groups such as alkylesters, arylesters,cycloalkylesters, and cycloarylesters. Preferred ester groups suitableas R¹ in the instant invention are selected from the group consisting ofethyl acetate, methyl acetate, n-propyl acetate, n-butyl acetate, phenylacetate, benzyl acetate, isobutyl benzoate, ethyl benzoate, ethylpropionate, ethyl stearate, ethyl trimethylacetate, methyl laurate, andethyl palmitate.

Preferred amino groups as R¹ in the compositions of this invention areexemplified by groups having the formula NR₂ wherein R is hydrogen or amonovalent hydrocarbon radical having from 1 to 20 carbon atoms such asaminoalkyl groups, aminoaryl groups, aminocycloalkyl groups, andaminocycloaryl groups. Preferred as amino groups in the instantinvention are groups such as amino, aminopropyl, ethylene diaminopropyl,aminophenyl, aminooctadecyl, aminocyclohexyl, propylene diaminopropyl,dimethylamino, and diethylamino.

Acetoxy groups suitable as R¹ in the compositions of the presentinvention are exemplified by groups having the formula--COOCH₃ such asacetoxyalkyl groups, acetoxyaryl groups, acetoxycycloalkyl groups, andacetoxycycloaryl groups. Preferred acetoxy groups in the compositions ofthe instant invention include acetoxy, acetoxyethyl, acetoxypropyl,acetoxybutyl, acetoxyphenyl, and acetoxycyclohexyl.

Sulfo groups which are preferred as R¹ in the compositions of thepresent invention are exemplified by groups having the formula SRwherein R is hydrogen or a monovalent hydrocarbon radical having from 1to 20 carbon atoms such as sulfoalkyl groups, sulfoaryl groups,sulfocycloalkyl groups, and sulfocycloaryl groups. Preferred sulfogroups include hydrogen sulfide, sulfopropyl, methylsulfopropyl,sulfophenyl, and methylsulfo.

Fluoro groups are exemplified by groups such as fluoroalkyl groups,fluoroaryl groups, fluorocycloalkyl groups, and fluorocycloaryl groups.Preferred fluoro groups which are suitable as R¹ in the compositions ofthis invention include fluoro, fluoropropyl, fluorobutyl,3,3,3-trifluoropropyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

Alkoxy groups suitable as R¹ in component (D) of this invention includegroups such as alkoxyalkyl groups, alkoxyaryl groups, alkoxycycloalkylgroups, and alkoxycycloaryl groups. Preferred alkoxy groups for R¹ inthe present invention are groups such as methoxy, ethoxy, butoxy,tertiary-butoxy, propoxy, isopropoxy, methoxyphenyl, ethoxyphenyl,methoxybutyl, and methoxypropyl groups.

Epoxy groups suitable as R¹ in component (D) of this invention includegroups such as epoxyalkyl groups, epoxyaryl groups, epoxycycloalkylgroups, and epoxycycloaryl groups. Preferred epoxy groups for R¹ in thepresent invention are groups such as epoxide, epichlorohydrin, ethyleneoxide, epoxybutane, epoxycyclohexane, epoxy ethylhexanol, epoxypropanol, and epoxy resin groups.

Acrylate groups suitable as R¹ in the formulae hereinabove includegroups such as acryloxyalkyl groups, acryloxyaryl groups,acryloxycycloalkyl groups, and acryloxycycloaryl groups. Preferredacrylate groups suitable as R¹ in the instant invention are selectedfrom the group consisting of acryloxyethyl, acryloxyethoxy,acryloxypropyl, acryloxypropoxy, methacryloxyethyl, methacryloxyethoxy,methacryloxypropyl, and methacryloxypropoxy.

Ether groups can also be used as R¹ in the formulae hereinabove. Theseether groups can include groups such as alkylethers, arylethers,cycloalkylethers, and cycloarylethers. Preferred ether groups suitableas R¹ in the instant invention are selected from the group consisting ofmethylethylether, methylpropylether, ethylmethylether, ethylethylether,ethylpropylether, methylphenylether, ethylphenylether,isopropylphenylether, tertiary-butylpropylether, methylcyclohexylether,and ethylcyclohexylether.

The olefinic hydrocarbon radicals of R¹ of the present invention mayhave from 2 to 20 carbon atoms. The olefinic hydrocarbon radicals arepreferably selected from the group consisting of the vinyl radical andhigher alkenyl radicals represented by the formula --R(CH₂)_(m) CH═CH₂wherein R denotes --(CH₂)_(n) -- or --(CH₂)_(p) CH═CH-- and m has thevalue of 1, 2, or 3, n has the value of 3 or 6, and p has the value of3, 4, or 5. The higher alkenyl radicals represented by the formula--R(CH₂)_(m) CH═CH₂ contain at least 6 carbon atoms. For example, when Rdenotes --(CH₂)_(n) --, the higher alkenyl radicals include 5-hexenyl,6-heptenyl, 7-octenyl, 8 -nonenyl, 9-decenyl, and 10-undecenyl. When Rdenotes --(CH₂)_(p) CH═CH--, the higher alkenyl radicals include, amongothers, 4,7-octadienyl, 5,8-nonadienyl, 5,9-decadienyl,6,11-dodecadienyl and 4,8-nonadienyl. Alkenyl radicals selected from thegroup consisting of 5-hexenyl, 7-octenyl, 9-decenyl, and 5,9-decadienyl,are preferred. It is more preferred that R denote --(CH₂)_(n) -- so thatthe radicals contain only terminal unsaturation and the most preferredradicals are the vinyl radical and the 5-hexenyl radical.

Specific examples of preferred polydiorganosiloxanes for use asComponent (E) in the compositions of the present invention include ViMe₂SiO(Me₂ SiO)_(x) SiMe₂ Vi , HexMe₂ SiO(Me₂ SiO)_(x) (MeHexSiO)_(y) SiMe₂Hex, ViMe₂ SiO(Me₂ SiO)_(x) (MeViSiO)_(y) SiMe₂ Vi, HexMe₂ SiO(Me₂SiO)₁₉₆ (MeHexSiO)₄ SiMe₂ Hex, HexMe₂ SiO(Me₂ SiO)₁₉₈ (MeHexSiO)₂ SiMe₂Hex, HexMe₂ SiO(Me₂ SiO)₁₅₁ (MeHexSiO)₃ SiMe₂ Hex, and ViMe₂ SiO(Me₂SiO)₉₆ (MeViSiO)₂ SiMe₂ Vi, HexMe₂ SiO(Me₂ SiO)_(x) SiMe₂ Hex,PhMeViSiO(Me₂ SiO)_(x) SiPhMeVi, HexMe₂ SiO(Me₂ SiO)₁₃₀ SiMe₂ Hex,ViMePhSiO(Me₂ SiO)₁₄₅ SiPhMeVi, ViMe₂ SiO(Me₂ SiO)₂₉₉ SiMe₂ Vi, ViMe₂SiO(Me₂ SiO)₈₀₀ SiMe₂ Vi, ViMe₂ SiO(Me₂ SiO)₃₀₀ SiMe₂ Vi, ViMe₂ SiO(Me₂SiO)₁₉₈ SiMe₂ Vi, vinyldimethylsiloxy-terminatedpoly((3,3,3-trifluoropropyl)methylsiloxy)pentasiloxane,vinylmethylsiloxy-terminated polydimethylsiloxane having(3,3,4,4,5,5,6,6,6-nonafluorobutyl)methylsiloxy functional groups,vinyldimethylsiloxy-terminated polydimethyldodecasiloxane having(3,3,3-trifluoropropyl) methylsiloxy groups,vinylmethylsiloxy-terminated polydimethylsiloxane having(3,3,4,4,5,5,6,6,6-nonafluorobutyl)methylsiloxy functional groups,dimethylhydridosiloxy-terminated poly((3,3,3-trifluoropropyl)methylsiloxy)pentasiloxane,dimethylhydroxysiloxy-terminated polydimethylsiloxane, anddimethylhydroxysiloxy-terminated dimethyl(aminoethylaminopropyl)methylsiloxane, wherein Me, Vi, Hex, and Ph denote methyl, vinyl, 5-hexenyland phenyl, respectively.

The amount of Component (E) employed in the compositions of the presentinvention varies depending on the amount of organohydrogensiloxane,rhodium catalyst, unsaturated acetate, and alcohol, that is employed. Itis preferred for purposes of this invention that from 1 to 99 weightpercent of (E), the organosilicon compound, be used, and it is highlypreferred that from 70 to 95 weight percent of (E) be employed, saidweight percent being based on the total weight of the composition.

The fiber treatment compositions of the instant invention can furthercomprise (F) a dispersant selected from the group consisting of one ormore surfactants and one or more solvents. The (emulsifying agents)surfactants are preferably of the non-ionic or cationic types and may beemployed separately or in combinations of two or more. Suitableemulsifying agents for the preparation of a stable aqueous emulsion areknown in the art. Examples of nonionic surfactants suitable as component(F) of the present invention include polyoxyethylene alkyl ethers,polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers andpolyoxyethylene sorbitan monoleates such as Brij™ 35L (from ICI AmericasInc., Wilmington, Del. 19897), Brij™ 30 (ICI Americas Inc., Wilmington,Del. 19897), and Tween™ 80 (ICI Americas Inc., Wilmington, Del. 19897),polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters,polyethylene glycol, polypropylene glycol, ethoxylated trimethylnonanolssuch as Tergitol® TMN-6 (from Union Carbide Chem. & Plastics Co.,Industrial Chemicals Div., Danbury, Conn. 06817-0001), andpolyoxyalkylene glycol modified polysiloxane surfactants. Examples ofcationic surfactants suitable as component (F) in the compositions ofthe instant invention include quaternary ammonium salts such asalkyltrimethylammonium hydroxide, dialkyldimethylammonium hydroxide,methylpolyoxyethylene cocoammonium chloride, and diplmitylhydroxyethylammonium methosulfate. Preferably, a combination of two orthree nonionic surfactants, or a combination of a cationic surfactantand one or two nonionic surfactants are used to prepare the emulsions ofthe present invention.

Examples of the preferred surfactants for use as Component (F) in thecompositions of this invention are the reaction products of alcohols andphenols with ethylene oxide such as the polyethoxyethers of nonyl phenoland octyl phenol and the trimethylnol ethers of polyethylene glycols,monoesters of alcohols and fatty acids such as glycerol monostearate andsorbitan monolaurate, and the ethoxylated amines such as thoserepresented by the general formula ##STR1## in which R"" is an alkylgroup having from about 12 to about 18 carbon atoms and the sum of a andb is from 2 to about 15. Silicone surfactants are also suitable for useas Component (F) in the instant invention. Preferred siliconesurfactants include silicone polyethers such as polyalkylpolyethersiloxanes and silicone glycol surfactants including silicone glycolpolymers and copolymers such as those disclosed in U.S. Pat. No.4,933,002, incorporated herein by reference. The emulsifying agents maybe employed in proportions conventional for the emulsification ofsiloxanes, from about 1 to about 30 weight percent, based on the totalweight of the composition.

Solvents may also be employed as Component (F) in the fiber treatmentcompositions of the instant invention. Preferred solvents for use asComponent (F) in the instant invention include hydrocarbon solvents suchas dichloromethane (methylene chloride) and acetonitrile. It ispreferred for purposes of the present invention that Component (F), thedispersant, be a mixture of water and one or more of the surfactantsdescribed hereinabove. It is also preferred that emulsification of thefiber treatment compositions of the instant invention is carried out byadding one or more emulsifying agents, and water be added to components(A), (B), (C), (D), and (E) described hereinabove and the resultingcomposition be subjected to high shear.

The amount of Component (F) employed in the compositions of the presentinvention varies depending on the amount of organohydrogensiloxane,rhodium catalyst, alcohol unsaturated acetate, and organosiliconcompound that is employed. It is preferred for purposes of thisinvention that from 0.25 to 99 weight percent of (F), the dispersant, beused, and it is highly preferred that from 1 to 95 weight percent ofdispersant be employed, said weight percent being based on the totalweight of the composition. When a surfactant is employed it is preferredthat from 0.25 to 20 weight percent be used, and when a solvent isemployed it is preferred that from 70 to 99.5 weight percent be used,said weight percent being based on the total weight of the composition.

The fiber treatment compositions comprising components (A), (B), (C),and (D) and optionally (E) and any surfactants or solvents (F) may beapplied to the fibers by employing any suitable application technique,for example by padding or spraying, or from a bath. For purposes of thisinvention, the compositions can be applied from a solvent, but ispreferred that the compositions be applied from an aqueous medium, forexample, an aqueous emulsion. Thus, any organic solvent can be employedto prepare the solvent-based compositions, it being understood thatthose solvents that are easily volatilized at temperatures of from roomtemperatures to less than 100° C. are preferred, for example, suchsolvents may include methylene chloride, acetonitrile, toluene, xylene,white spirits, chlorinated hydrocarbons, and the like. The treatingsolutions can be prepared by merely mixing the components together withthe solvent. The concentration of the treating solution will depend onthe desired level of application of siloxane to the fiber, and on themethod of application employed, but it is believed by the inventorsherein that the most effective amount of the composition should be inthe range such that the fiber (or fabric) picks up the siliconecomposition at about 0.05% to 10% on the weight of the fiber or fabric.According to the instant method of treatment, the fibers usually in theform of tow, or knitted or woven fabrics, are immersed in an aqueousemulsion of the compositions whereby the composition becomes selectivelydeposited on the fibers. The deposition of the composition on the fibersmay also be expedited by increasing the temperatures of the aqueousemulsion, temperatures in the range of from 20° to 60° C. beinggenerally preferred.

Preparation of the aqueous emulsions can be carried out by anyconventional technique. The fiber treatment compositions of this can beprepared by homogeneously mixing Components (A), (B), (C) and (D) andany optional components in any order. Thus it is possible to mix allcomponents in one mixing step immediately prior to using the fibertreatment compositions of the present invention. Most preferably (A),(B), and (C), are emulsified and then (D) and/or (E) is emulsifiedindividually and the two emulsions thereafter combined and then anyoptional components added. The emulsions of the present invention may bemacroemulsions or microemulsions and may also contain optionalingredients, for example antifreeze additives, preservatives, biocides,organic softeners, antistatic agents, dyes and flame retardants.Preferred preservatives include Kathon® LX(5-chloro-2-methyl-4-isothiazolin- 3-one from Rohm and Haas,Philadelphia, Pa. 19106), Giv-gard® DXN(6-acetoxy-2,4-dimethyl-m-dioxane from Givaudan Corp., Clifton N.J.07014), Tektamer® A.D. (from Calgon Corp., Pittsburgh, Pa. 152300),Nuosept® 91,95 (from Huls America, Inc., Piscataway, N.J. 08854),Germaben® (diazolidinyl urea and parabens from Sutton Laboratories,Chatham, N.J. 07928), Proxel® (from ICI Americas Inc., Wilmington, Del.19897), methyl paraben, propyl paraben, sorbic acid, benzoic acid, andlauricidin.

Following the application of the siloxane composition the siloxane isthen cured. Preferably, curing is expedited by exposing the treatedfibers to elevated temperatures, preferably from 50° to 200° C.

The fiber treatment compositions of this invention can be employed forthe treatment of substrates such as animal fibers such as wool,cellulosic fibers such as cotton, and synthetic fibers such as nylon,polyester and acrylic fibers, or blends of these materials, for example,polyester/cotton blends, and may also be used in the treatment ofleather, paper, and gypsum board. The fibers may be treated in any form,for example as knitted and woven fabrics and as piece goods. They mayalso be treated as agglomerations of random fibers as in fillingmaterials for pillows and the like such as fiberfil.

The fiber treatment composition of components (A), (B), (C), and (D) andany optional components should be used at about 0.05 to 25 weightpercent in the final bath for exhaust method applications, and about 5gm/l to 80 gm/l in a padding method of application, and about 5 gm/l to600 gm/l for a spraying application. The compositions employed in thisprocess are particularly suitable for application to the fibers orfabrics from an aqueous carrier. The compositions can be made highlysubstantive to the fibers, that is they can be made to depositselectively on such fibers when applied thereto as aqueous emulsions.Such a property renders the compositions particularly suited for aqueousbatch treatment by an exhaustion procedure, such exhaustion proceduresbeing known to those skilled in the art. The compositions of the instantinvention are new and novel and provide a fast cure and wide curetemperature ranges for curing them on fibers or fabrics compared to thecompositions of the prior art, having a temperature cure range of from50° C. to 200° C. Further, the fibers have superior slickness and nooily feeling after cure. The compositions of the instant inventionprovide consistent performance, good bath life of more than 24 hours at40° C., have good laundry and dry cleaning durability, and have verygood suitability for application by spraying.

Fiber Slickness was tested by using a DuPont(R) unslickened fiberfilproduct, such as Hollofil® T-808, for the evaluation of slicknessimparted by the application of the silicone emulsion of the presentinvention. A piece of Hollofil® T-808 is soaked in the diluted emulsionof interest and then passed through a roller to obtain 100% wet-pickup,i.e., the weight of the finished fiberfil is twice that of theunfinished fiberfil. After drying at room temperature, the finishedsample is heated at 200° C. for 2-25 minutes. Thus prepared, thefinished fiberfil usually contains approximately the same silicone levelas that of the emulsion of interest.

The slickness of fiberfil is measured by staple pad friction which isdetermined from the force required to pull a certain weight over afiberfil staple pad. The staple pad friction is defined as the ratio ofthe force over the applied weight. A 10 pound weight was used in thefriction measurement. A typical instrument set-up includes a frictiontable which is mounted on the crosshead of an Instron tensile tester.The friction table and the base of the weight are covered with EmeryPaper #320 from the 3M Company so that there is little relative movementbetween the staple pad and the weight or the table. Essentially all ofthe movement is a result of fibers sliding across each other. The weightis attached to a stainless steel wire which runs through a pulleymounted at the base of the Instron tester. The other end of thestainless steel wire is tied to the loadcell of the Instron tester.

Following are examples illustrating the compositions and methods of thepresent invention. In the examples hereinbelow, THF denotestetrahydrofurfuryl, and THFA denotes tetrahydrofururyl alcohol.

EXAMPLES 1-8

In order to illustrate the effectiveness of the catalyst compositions ofthe invention the following tests were conducted. A rhodium catalystcomplex was prepared by dissolving RhCl₃.6H₂ O in a complexing solvent.This solution was then added at 6 parts per million (ppm) to a mixtureof 100 gm of a trimethylsilyl terminated polymethylhydrogensiloxanehaving a viscosity of 30 centistokes at a temperature of 25° C. andhaving the formula Me₃ SiO(MeHSiO)₇₀ SiMe₃ and 10 gm of Linallylacetate. The final formulation was placed in a 50° C. air oven andwatched for 168 hours or until it gelled. The type of complexing solventand the number of hours the sample took to gel is recorded in Table Ihereinbelow.

                  TABLE I                                                         ______________________________________                                        Ex-                                Hours to                                   am-                                Gel 50° C.                          ple  Rhodium    Complexing Solvent Air Oven                                   ______________________________________                                        1    RhCl.sub.3.6H.sub.2 O                                                                    Tetrahydrofuran    16                                         2    RhCl.sub.3.6H.sub.2 O                                                                    2,5-Dimethyltetrahydrofuran                                                                      16                                         3    RhCl.sub.3.6H.sub.2 O                                                                    Tetrahydro-3-furan methanol                                                                      passed 168                                 4    RhCl.sub.3.6H.sub.2 O                                                                    Furfuryl alcohol   passed 168                                 5    RhCl.sub.3.6H.sub.2 O                                                                    Tetrahydrofurfuryl alcohol                                                                       passed 168                                 6    RhCl.sub.3.6H.sub.2 O                                                                    Benzyl alcohol     72                                         7    RhCl.sub.3.6H.sub.2 O                                                                    1,4-Butanediol     84                                         8    RhCl.sub.3.6H.sub.2 O                                                                    Methanol           <1                                         ______________________________________                                    

It is clear from Table I that the rhodium catalyst complexes containingalcohols having greater than 3 carbon atoms outperformed the catalystswhich do not contain an alcohol or which contain an alcohol having lessthan 3 carbon atoms by remaining stable for a much longer period oftime.

EXAMPLES 9-11

In order to illustrate the effectiveness of the fiber treatmentcompositions of the present invention the following tests wereconducted. A 0.03 molar rhodium catalyst solution was prepared bydissolving 1 gram of RhCl₃.6H₂ O (rhodium trichloride hexahydrate) in120 grams of THFA.

Into a glass container was added the unsaturated acetate (in this caselinallyl acetate). With gentle mixing using a round edge three bladeturbine mixing impeller, the rhodium catalyst solution prepared abovewas added to the unsaturated acetate and mixed until the mixture washomogenous. Next, 100 grams of a trimethylsilyl terminatedpolymethylhydrogensiloxane having a viscosity of 30 centistokes at atemperature of 25° C. and having the formula Me₃ SiO(MeHSiO)70SiMe₃ wasadded to the mixture and stirred gently until the mixture was againhomogenous. This was followed by adding about 1.78 grams of a methylenechloride solvent, and about 38 grams of water containing up to 0.22grams of a preservative (sorbic acid) to the mixture. Mixing was thenresumed at medium speed for 20 to 30 minutes. The mixture was thenprocessed through a high shear device to produce the emulsions of theinstant invention. The particle sizes of the emulsions ranged from 0.7to 3.0 microns and the pH of the emulsions ranged from 3.0 to 4.5.

A relative ranking from 1 to 10 was established using known commercialfinishes based upon slickness values obtained using the Staple PadFriction frictional test described hereinabove. No finish was given aranking of 1, the commercial finish was given a ranking of 6, and apremium finish was given a ranking of 10. The amount of acetate, acetatetype, the amount of catalyst, catalyst type, the time it took the sampleto cure in minutes (min.), and the performance of each example arereported in Table II hereinbelow.

                  TABLE II                                                        ______________________________________                                        Ex-  Ace-            Cat-                                                     am-  tate   Acetate  alyst Catalyst  Cure                                     ple  (g)    Type     (g)   Type      (Min.)                                                                              Rating                             ______________________________________                                         9   3      Linallyl 0.3   RhCl.sub.3, THFA                                                                        3     10                                 10   2      Linallyl 0.2   RhCl.sub.3, THFA                                                                        3     10                                 11   3      Linallyl 0.1   RhCl.sub.3, THFA                                                                        3     10                                 ______________________________________                                    

The examples hereinabove show that fiber treatment compositionscontaining the rhodium catalyst complexes of the instant invention gavesuperior slickness results.

EXAMPLE 12

In order to illustrate the effectiveness of the fiber treatmentcompositions of the present invention the following test was conducted.A 0.03 molar rhodium catalyst solution was prepared by dissolving 1 gramof RhCl₃.6H₂ O (rhodium trichloride hexahydrate) in 120 grams of THFA.

Into a glass container was added 4 grams of linallyl acetate. Withgentle mixing using a round edge three blade turbine mixing impeller,0.1 grams of the rhodium catalyst solution prepared above was added tothe acetate and mixed until the mixture was homogenous. Next, a mixtureof 100 grams of a trimethylsilyl terminated polymethylhydrogensiloxanehaving a viscosity of 30 centistokes at a temperature of 25° C. andhaving the formula Me₃ SiO(MeHSiO)₇₀ SiMe₃ and 10 grams of a 250 cpspolydimethylsiloxane having 8% pendant alkylsulfocarboxy moieties wasadded to the mixture and stirred gently until the mixture was againhomogenous. This was followed by adding about 1.78 grams of apolyoxyethylene lauryl ether surfactant, and about 38 grams of watercontaining up to about 0.22 grams of a preservative (sorbic acid) to themixture. Mixing was then resumed at medium speed for 20 to 30 minutes.The mixture was then processed through a high shear device to producethe emulsions of the instant invention. The particle sizes of theemulsions ranged from 0.7 to 3.0 microns and the pH of the emulsionsranged from 3.0 to 4.5.

The sample was ranked as described hereinabove and was obtained usingthe Staple Pad Friction frictional test described hereinabove. Thesample took 10 minutes to cure and had a slickness value of 10.

This example show that the catalysts of the instant invention whenincorporated into a fiber treatment composition containing organosiliconcompounds cure into fiber treatment compositions to give good slicknessratings.

Comparison Example I

A silicone composition was prepared according to the disclosure ofRevis, U.S. Pat. Nos. 4,954,401, 4,954,597, and 5,082,735. A 0.03 molarrhodium catalyst solution was prepared by dissolving 1 gram of RhCl₃.6H₂O (rhodium trichloride hexahydrate) in 120 grams of THF. Into a glasscontainer was added 5 grams of allyl acetate. With gentle mixing using around edge three blade turbine mixing impeller, 0.1 grams of thecatalyst solution prepared above was added to the acetate and mixeduntil the mixture was homogenous. Next, 100 grams of a trimethylsilylterminated polymethylhydrogensiloxane having a viscosity of 30centistokes at a temperature of 25° C. and having the formula Me₃SiO(MeHSiO)₇₀ SiMe3 was added to the mixture and stirred gently untilthe mixture was again homogenous. Next, 4 grams of this mixture wasadded to 96 grams of water. This mixture was then stirred for 20 to 30minutes.

The sample was ranked as described hereinabove and was obtained usingthe Staple Pad Friction frictional test described hereinabove. Thesample took 10 minutes to cure and had a slickness value of 2. Thus incomparison to the compositions of the instant invention that fibertreatment compositions not containing the catalyst compositions of theinstant invention gave much poorer results.

Comparison Example II

A silicone composition was prepared according to Example 2 of Revis,U.S. Pat. No. 4,954,401. A catalyst was prepared according Example 1 ofRevis, U.S. Pat. No. 4,954,401, by stirring 10 grams of RhCl₃.3H₂ O in1200 grams of THF at room temperature for about 12 hours. A mixture of2.0 grams of trimethylsilyl terminated polymethylhydrogensiloxane havinga viscosity of 30 centistokes at a temperature of 25° C., 3.5 grams ofallyl acetate, and 0.02 grams of catalyst was combined and stirredgently until the mixture was homogenous.

The sample was ranked as described hereinabove and was this rankingobtained using the Staple Pad Friction frictional test describedhereinabove. The sample took 10 minutes to cure and the sample fiberswere fused together and became extremely brittle thus preventing thedetection of a slickness value (i.e. the sample failed). Thus incomparison to the compositions of the instant invention, compositionswhich did not contain the catalyst of the instant invention gave muchpoorer results than do the compositions of the instant invention.

Comparison Example III

A silicone composition was again prepared according to Example 2 ofRevis, U.S. Pat. No. 4,954,401. A catalyst was again prepared accordingExample 1 of Revis, U.S. Pat. No. 4,954,401, by stirring 10 grams ofRhCl₃.3H₂ O in 1200 grams of THF at room temperature for about 12 hours.The amounts of the ingredients in this example were varied however. Inthis example a mixture of 100 grams of trimethylsilyl terminatedpolymethylhydrogensiloxane having a viscosity of 30 centistokes at atemperature of 25° C., 10 grams of allyl acetate, and 0.1 grams ofcatalyst was combined and stirred gently until the mixture washomogenous.

The sample was again subjected to the tests described hereinabove.Again, the sample took 10 minutes to cure and the sample fibers werefused together and became extremely brittle thus preventing thedetection of a slickness value (i.e. the sample failed). Thus incomparison to the fiber treatment compositions of the instant inventioncontaining the novel rhodium catalyst complex of this invention,compositions which do not contain an alcohol having at least 3 carbonatoms gave much poorer results.

Comparison Example IV

A first emulsion was prepared in the following manner. About 2 weightpercent of an aqueous solution of a mixture of two partially hydrolyzedPVA's (polyvinyl alcohols) having a degree of hydrolysis of 88% and a 4%aqueous solution viscosity of 5 centipoise (cP) and 24 centipoise (cP)at 25° C., respectively, and about 0.3 weight percent of apolyoxyethylene (10) nonyl phenol surfactant was mixed with 28 weightpercent of water. Next, 13.5 weight percent of anorganohydrogenpolysiloxane having the formula Me₃ SiO(MeHSiO)₅ (Me₂SiO)₃ SiMe₃, and 28 weight percent of a dimethylvinylsiloxy-terminatedpolydimethylmethylvinylsiloxane having a viscosity of 350 cP were mixedand stirred. Next, the PVA-surfactant mixture was added to the siloxanemixture and stirred. This mixture was then processed through a colloidmill and diluted with 28 weight percent of water containing a biocide toform an emulsion.

A second emulsion was prepared by mixing 2 weight percent of an aqueoussolution of a mixture of two partially hydrolyzed PVA's (polyvinylalcohols) having a degree of hydrolysis of 88% and a 4% aqueous solutionviscosity of 5 centipoise (cP) and 24 centipoise (cP) at 25° C.,respectively, about 0.3 weight percent of a polyoxyethylene (10) nonylphenol surfactant, and 28 weight percent of water. Next, about 40 weightpercent of dimethylvinylsiloxy-terminatedpolydimethylmethylvinylsiloxane having a viscosity of 350 cP and about1% of a platinum-containing catalyst were mixed and stirred. Next, thePVA-surfactant mixture was added to the siloxane mixture and stirred.This mixture was then processed through a colloid mill and diluted with28 weight percent of water containing a biocide to form an emulsion.

Next, 7.5 grams of the first emulsion, 7.5 grams of the second emulsion,and 85 grams of water were mixed together and the resulting emulsionstirred.

This silicone emulsion cured in 10 minutes and the sample was rankedaccording to the staple pad friction procedure delineated hereinabove.The silicone emulsion attained a rating of between 4 and 5.

Comparison Example V

A silicone emulsion was prepared according to the disclosure of Bunge inU.S. Pat. No. 4,954,554. A first emulsion was prepared in the followingmanner. About 38 weight percent of a dimethylvinylsiloxy-terminatedpolydimethylsiloxane having a viscosity of 450 centistokes (cst) and 2weight percent of a mixture of an organohydrogenpolysiloxane having theformula Me₃ SiO(MeHSiO)₅ (Me₂ SiO)₃ SiMe₃ and adimethylsiloxanemethylhydrogensiloxane having a viscosity of 85centistokes (cst) were mixed and stirred. About 2 weight percent of anaqueous solution of an intermediately hydrolyzed PVA having a degree ofhydrolysis of 96% and a 4% aqueous solution viscosity of 30 centipoise(cP) at 25° C., a surfactant, and 29 weight percent of water were mixedand stirred. Next, the PVA-surfactant mixture was added to the siloxanemixture and stirred. This mixture was then processed through a colloidmill and diluted with 29 weight percent of water containing a biocide toform an emulsion.

A second emulsion was prepared by mixing about 2 weight percent of anaqueous solution of an intermediately hydrolyzed PVA having a degree ofhydrolysis of 96% and a 4% aqueous solution viscosity of 30 centipoise(cP) at 25° C., a surfactant, and 51 weight percent of water. Next,about 40 weight percent of a dimethylvinylsiloxy-terminatedpolydimethylsiloxane having a viscosity of 450 cP and about 1% of aplatinum-containing catalyst were mixed and stirred. Next, thePVA-surfactant mixture was added to the siloxane mixture and stirred.This mixture was then processed through a colloid mill and 7 weightpercent of water containing a biocide was added to form an emulsion.

Next, 7.5 grams of the first emulsion, 7.5 grams of the second emulsion,and 85 grams of water were mixed together and the resulting emulsionstirred.

This silicone emulsion cured in 10 minutes and the sample was rankedaccording to the staple pad friction procedure delineated hereinabove.The silicone emulsion attained a rating of between 5 and 6. Thus thecompositions of the instant invention outperformed the siliconeemulsions previously described in the art.

It should be apparent from the foregoing that many other variations andmodifications may be made in the compounds, compositions and methodsdescribed herein without departing substantially from the essentialfeatures and concepts of the present invention. Accordingly it should beclearly understood that the forms of the invention described herein areexemplary only and are not intended as limitations on the scope of thepresent invention as defined in the appended claims.

That which is claimed is:
 1. A catalyst composition comprising:(A) arhodium catalyst; (B) an allyl ester, vinyl ester, or unsaturatedacetate; and (C) an alcohol having 3 or more carbon atoms.
 2. Acomposition according to claim 1, wherein (A) is selected from the groupconsisting of RhCl₃, RhBr₃, and RhI₃.
 3. A composition according toclaim 1, wherein (A) is selected from the group consisting of RhCl₃.nH₂O, RhBr₃.nH₂ O, Rh(NO₃)₃.nH₂ O, and Rh(SO₄)₃.nH₂ O, and n has a value offrom 1 to
 10. 4. A composition according to claim 1, wherein (B) isselected from the group consisting of allyl acetate, linallyl acetate,and isopropenyl acetate.
 5. A composition according to claim 1, wherein(C) is selected from the group consisting of C₃ and greater diols,furans having at least one OH group per molecule, and pyrans having atleast one OH group per molecule.
 6. A composition according to claim 5,wherein the diols are selected from the group consisting of1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol,1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol,1,5-hexanediol, 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol,1,10-decanediol, and 2-phenyl-1,2-propanediol.
 7. A compositionaccording to claim 1, wherein (C) is selected from the group consistingof 1-heptanol, benzyl alcohol, 1-octanol, 1-nonanol, 1-decanol,undecylenyl alcohol, 2,4-dichlorobenzyl alcohol, phenethyl alcohol,1-undecanol, 2-methylbenzyl alcohol, 3-methylbenzyl alcohol, and2-phenyl-1-propanol.
 8. A composition according to claim 5, wherein thefurans are selected from the group consisting of 5-methyltetrahydrofuran-2-methanol, 2-hydroxy-2-(hydroxymethyl)tetrahydrofuran,dihydro-5-(hydroxymethyl)-2-(3H)-furone, tetrahydro-3-furanmethanol,furfuryl alcohol, and tetrahydrofurfuryl alcohol.
 9. A compositionaccording to claim 5, wherein the pyran is tetrahydropyran-2-methanol.10. A composition according to claim 1, wherein (B) is selected from thegroup consisting of allyl butyrate, allyl acetate, linallyl acetate,allyl methacrylate, vinyl acetate, allyl acrylate, vinyl butyrate,isopropenyl acetate, vinyl trifluoroacetate, 2-methyl-1-butenyl acetate,vinyl 2-ethyl hexanoate, vinyl 3,5,5-trimethylhexanoate, allyl3-butenoate, bis-(2-methylallyl) carbonate, diallyl succinate, and ethyldiallylcarbamate.